Fluid galvanizing blanket



Patented June 8, 1948 toDewey and Almy.Chemical;Company,North" Cambridge, Mass, a corporation of'Massachu setts NoDrawing. Application February 1, 1947, Serial No. 725 975- 6 Claims.

The present application is acontinuation-inpart of Serial No.-428,62=9,-fi1ed January'28; 1942, now abandoned.-

The large-open surface of-agalvanizing kettle allows such rapid oxidation of the melted Zinc that-itisnecessary-to shut offas much air as possible from reaching the-melted surface. A solid=-coveris notpractical-when large shapes and pipes must be fed into the zinc. Consequently, it" is customary toprotect the molten zinc surface'with a floating blanket of some loose orpowderymaterial,such; forinstance, as granu= lated eh'arcoalsaw dust, leather scrap, exfoliatedvermiculite,etc;, whichreduces the oxidation of the-metal andalso-reduces the-loss of heat from the metal 'surfaceybut a blanket-of loose mate rial permits-some air to reach the surface of the zinc; interferes with feeding wire into the kettle and is'ex'tremely inconvenient whenever the kettle must bedfossed.

To avoid thetroubleswhich loose solid matter inherentlycauses, at least oneattempt has-been made to "produce a-li'quid blanket, but, for reasons which will be explained, the composition has not.beenoused' commercially to any substantial extent. That blanket is composed of sodium chloride, potassium chloride and-zinc-chloride with or without magnesium chloride. Although the ingredients are in proper proportion toform a eutectic below the melting point of zinc, the separate ingredients :do not fuse properly while floating: 'on melted'zinc. Therefore; as a practical matter, it was found necessary to fuse the ingredients separately, usually at about 1000 F., allow th'e-fused mixturetocool, and then grind the resultant mass before application to the bath. This procedure had to be performed either by the manufacturer of'the crystals, in which case it increased the: expense, or by the galvanizer, in whichcase it required equipment with? which the galvanizer'was not ordinarily provided. lneither case, aisub'stanti alitem of expense was incurred. In'"thesecond place, such a blanket gave on hydrochloric acidfumes which are aserious menace to the health of the operators and cause corrosion ofmetals; expensive protective measures-andconstant attention wererequired toremove them sufliciently to prevent serious injury.

In the thirdpl'ace, the zinc oxide, which constantlyl'forms during'the operation of thebatl i, accumulatedin the molten blanket and graduallystiffned it. A thickblanket could-be thinned (by'simple dilution) by, the addition -offresh crystalsto it; but even then, the accumulation of zinc'oxide became so great that the blanket had to'be removed and a new blanket substituted in a comparatively short time. Since the blanket, when'removed, contained asmuch as 60% of zincythe' 'losswas substantial evenifithe. zinc was recovered? Y I have discovered that it is possible-to providea' dry, granular'blanket compound which fuses quicklyand completely'ywhile fl'oating upon the melted zinc "in a galvanizers kettle-so that prefusion' and grinding isnot required; which gives off alkaline (ammonia) fumes and, therefore; requires 'no protection ofemployees and machinery and which canbe regenerated from time to time by the addition of small amounts of-- a' regenerative composition whichconverts the-zinc oxide into zinc chloride.- I stiflfens the blanket. Its-conversion to'zinc'ehlo ride, which is fluid at molten zinc temperatures, produces ablanket whichcan=beused indefinitely, hence the loss from discarded blankets is greatly reduced.

My improved compoundcomprises essentially-amixture of an" alkali-metal chloride -(preferably potassium chloride) zinc" chloride; ammonium chloride'and' '-preferably-'a -small amount of' -zinc oxide, the proportions of ammoniumchloride; alkali-metalchlorideand zin'c'ch'loride being such as to"give-an'*initialfiision"point far belowthat of zinc, and the proportion-of alk'ali metal -'chloride tothe zinechloride-being such as to maintain' the fluidityof the blanketafter th'e partial or complete exhaustion of the ammonium chloride. Furthermore," as-zi-nc oxide, and to some extent} zinc" oxyehlorid,- accumulate in-- the blanket; theycan' be" converted- -into additional zincchlorideby the addition of a regenerative compound 'which='consistsof the-materials of the original blanket butin which the ammonium chloride'is' much in excess of theoriginal proportion.

I believethat the effective melting of 'my composition on' a zinc bath" is due to a combination ofthe followin'gacti-ons:

1; The reaction' ofzinc oxide and ammonium chloride releases-water; therefore, all salts first tend to go intowater solution.

2. Even small additions of [ammonium chlorideto zinc chloridelower the'meltingpoint of the mixture "with" extreme rapidity. For example, although 'zinc" chloride melts at 503.6 E, a mixture of zinc chloride and 16.39 of ammonium chloride-meltsat 450-F If"the-proportio'nof ammonium chloride-is raised to:26.- the melting'point falls to 36 79" 3. As*thetemperature-rises; and water bails out; the release of steam churns the whole -mass thoroughly; sothat fusion takesplace-more rapidly.

4; The-zinc oxidein-the compoundor'that formed bythe zinc; bath" itself- -'reacts with the ammonium-chlc'irideand"'produces"ammonia and additionalizinc chloride; Onlyf ammonia I fumes are" released from the blanket? chloride andzinc'chloride maintains the liquidity It is -zincoxide which of the blanket. Accordingly, it is possible to maintain the fusion point of the material of which the blanket is formed below that of zinc and the subliming point of ammonium chloride.

When the compound embodying my invention is placed on the top of the molten Zinc bath, it melts immediately, foaming but not sputtering as the water is given off, and then settling down to a very fluid layer. The ammonia gas given off is in small quantities and is not objectionable. I Even with a liquid blanket which seals the surface from air, there is an unavoidable formation of zinc oxide while the kettle is in operation. Pipes dropped into the bath carry in air, oxide forms beyond the exit dam. Water carried in as flux solution on the steel forms some oxide, but its main effect is to form zinc oxychloride or oxychloride-like bodies which ultimately build up as lumps in the blanket. These may be removed by straining the blanket through a wire basket skimmer. The zinc oxide, although concentrating in the blanket, remains well distributed. It cannot be removed mechanically. Consequently, as its concentration rises, the blanket stifiens until it becomes too pasty for articles to be fed into the kettle properly.

I have discovered that the blanket may be regenerated to overcome the accumulation of oxides and so used indefinitely by the addition of a second compound comprising essentially an alkali-metal chloride, (preferably potassium chloride), and ammonium chloride, with or without zinc oxide, the proportion of ammonium chloride being very much in excess of the proportion of ammonium chloride in the original blanket. Zinc chloride is also usually included in the regenera tion compound, since it must be present durin fusion to prevent sublimation of the ammonium chloride before fusion. However, where the metal to be coated has been fluxed with zinc chloride the amount in the blanket may be reduced or omitted altogether as explained hereinafter. This is not the mere addition of more of the original blanket forming material which, of course, would tend to increase the liquidity of the blanket because of dilution. On the contrary, the relatively large amount of ammonium chloride unites with the zinc oxide which would otherwise stiffen the blanket and converts the oxide into zinc chloride which has the opposite effect and tends to liquefy the blanket.

In the regeneration operation, the attempt should be made to maintain the concentration of alkali-metal chloride approximately in the proportions existing in the original blanket composition so that the low-fusing, eutectic mixture of zinc-chloride-alkali metal chloride will be maintained. There also should be enough zinc chloride present to form a low-fusing mixture with the ammonium chloride and so prevent the loss of ammonium chloride by sublimation. However, some fluxing practices continuously add zinc chloride to the bath in the form of flux on the steel. When sufiicient zinc chloride is added in this manner, it is unnecessary to add zinc chloride as an ingredient in the regenerative composition. Zinc oxide may or may not be added. If used, its function is to prevent caking of the regenerative crystals. Zinc oxide is, of course, important to prevent the release of acid fumes, but if caking of the crystals is not a consideration, enough zinc oxide exists in the blanket itself at the time when regeneration is necessary to prevent acid from being released.

The ammonium chloride not only'reacts with the zinc oxide, but with the zinc oxychloride. I have found it much better and therefore recommend that the regenerative compound be added frequently and in small quantities so that it may unite with the oxychlorides and retard the formation of lumps which ammonium chloride cannot penetrate. When the regenerative compound is added infrequently, the lumps are quite large before the next addition is made, consequently the compound is less effective in retarding the growth of the lumps.

My preferred composition for the blanket is as follows:

Parts by weight Potassium chloride 3 Zinc chloride 59.3 Ammonium chloride 4. Zinc oxide 1.1

I have included zinc oxide in the above formula because it is advantageous since it prevents caking of the crystals and prevents the production of acid fumes.

This composition begins to melt at 270 F. It increases in viscosity at 340 F. to 360 F. when the last traces of water are expelled, but is a thin liquid at 420. to 450 F. On cooling, it congeals at 400 F. The potassium chloride, it will be noticed, is in excess of that necessary to give a eutectic mixture with zinc chloride at 400 F. This affords an excess to fuse with any zinc chloride which comes into the blanket as flux on the steel. The excess has been determined by practice to be sufficient to compensate for dilution of the blanket by zinc chloride from the flux.

Another satisfactory formula for the original blanket made with zinc-ammonium chloride is as follows:

Parts by weight Potassium chloride 35. Zinc ammonium chloride 10.9 Zinc chloride 53. Zinc oxide 1.1

The following compositions give a wide range of adjustment and meet nearly all commercial conditions:

EXAMPLES or ORIGINAL BLANKET COMPOSITIONS I II III IV V VI 6 4. 6 4. 6 l0 l0 l0 Ratio of alkali metal chloride to zinc chloride 37:63 45:55 15:85 30:70 20:80 40:60

Both the ammonium chloride and the zinc oxide may be much in excess of the amounts already suggestedthe ammonium chloride may be as much as 20 percent and the zinc oxide may be as much as 15 percent of the total composition-but the ammonium chloride should always be in excess of the zinc oxide since there should be enough to convert most of the zinc oxide into zinc chloride.

The regenerative compositions may vary and should be adjusted to the individual galvanizers practice to allow for fiuxing materials carried'into the blanket.

REGENERATIVE COMPOUNDS Formulas (parts by weight) The ammonium chloride should be at least 9%.

In the foregoing examples the proportions are specified in parts by weight of the respective materials.

Formula A above has been found satisfactory for use for pipe or wire under a wide variety of conditions. It will be noticed that it contains about equal amounts of zinc ammonium chloride and zinc chloride.

Formula B is also satisfactory for general use but is ordinarily slightly more expensive, although it has the advantage of being completely non-hygroscopic, It contains no separate zinc chloride or ammonium chloride, but only the double salt.

Formula C is used where the flux on the articles to be galvanized deposits in the bath zinc chloride to such an extent that it is undesirable to add zinc chloride in the regenerative compound. Certain galvanizers make a practice of using saturated solutions of zinc chloride in the flux and in this case an excess of zinc chloride accumulates in the bath, making the use of zinc chloride in the regenerative compound undesirable.

Formula D is a regenerative compound suitable for use with an original blanket like my preferred composition which contains KCl 35, ZnClz 59.3, NH4C1 4.6 and ZnO 1.1 and is for use where the flux employed consists of the common zinc ammonium chloride known as galvanizers crystals and which has 1 mol of zinc chloride and 3 mole of ammonium chloride.

Formula E is for use with an original blanket made in accordance with Example IV above.

In describing my invention and in the claims, I have referred to zinc chloride and ammonium chloride, treating them as if they were always separate substances. It will be understood, however, that the two separate salts may be replaced with proper quantities of the double salts (zinc ammonium chlorides).

Although sodium and lithium chloride may be used in place of potassium chloride, I prefer to use potassium chloride because lithium chloride is too expensive and the crystals of sodium chloride decrepitate prior to fusion causing sputtering in the blanket, while potassium chloride melts quietly without sputtering.

I claim:

1. A blanket forming compound initially fusible upon molten zinc baths which comprises potassium chloride about 35 percent, ammonium chloride about 4.6 percent, Zinc oxide about 1.1 percent, and zinc chloride about 59.3 percent.

2. A blanket forming compound initially fusible upon molten zinc baths which comprises ammonium chloride 4.6 to 20 percent, zinc oxide 1.1 to 15 percent, and the balance essentially alkali metal chloride and zinc chloride in proportions between 15:85 and 45:55, and the ammonium chloride being in excess of the zinc oxide.

3. A regenerating compound for fusible blankets for molten zinc baths, which blankets are composed initially and essentally of potassium chloride, zinc chloride and ammonium chloride, said regenerating compound consisting of ammonium chloride at least 9 percent and not more than 60% and the balance essentially alkali metal chloride.

4. A regenerating compound for fusible blankets for molten zinc baths, which blankets are composed initially and essentially of potassium chloride, zinc chloride and ammonium chloride, said regenerating compound consisting of ammonium chloride at least 9 percent and not more than 60% and the balance essentially alkali metal chloride and zinc chloride.

5. In the method :of protecting the surface of molten zinc in the galvanizing of metal the steps which comprise adding a dry mix consisting essentially of alkali metal chloride, zinc chloride, ammonium chloride and a small amount of zinc oxide, the proportions of ammonium chloride, zinc chloride and alkali metal chloride being such as to IDI'OdllCe a fusion blanket on the surface of the molten zinc, and the proportions of alkali metal chloride to zinc chloride in the mix being such as to maintain the fluidity of the blanket after the exhaustion of the ammonium chloride, and maintaining the fluidity of the blanket by the periodic addition of a composition consisting essentially of at least 9 percent of ammonium chloride and the balance alkali metal chloride.

6. In the method of protecting the surface of molten zinc in the galvanizing of metal, the steps which comprise adding a dry mix of ammonium chloride 4.6 to 20 percent, zinc oxide 1.1 to 15 percent, and the balance essentially alkali metal chloride and zinc chloride in the proportions between 15:85 and 45:55, which mix forms a liquid fusion blanket on the surface of the molten zinc, and maintaining the fluidity of the blanket by the periodic addition of a composition consisting essential-ly of at least 9 percent of ammonium chloride and the balance alkali metal chloride and zinc chloride.

DUNBAR L. SHANKLIN.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 92,998 Peake July 27, 1869 1,293,823 Luckey Feb, 11, 1912 1,560,933 Emura Nov. 10, 1925 1,914,269 Liban June 13, 1933 2,012,809 Derick Aug. 27, 1935 OTHER REFERENCES 1939 Metals Handbook, Amer. Soc. for Metals, Cleveland, page 1206.

International Critical Tables, National Research Council, published 1928 by McGraw-Hill Book 00., New York, vol. IV, page 45.

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